仿真饰品中邻苯二甲酸酯类增塑剂的含量测定和迁移风险考察

建立了仿真饰品中14种邻苯二甲酸酯类增塑剂的含量和迁移量测定的气相色谱-质谱(GC-MS)检测方法。考察了微波萃取、超声波萃取、快速溶剂萃取和索氏提取4种前处理方法对增塑剂含量测定的影响。在模拟人体温度及汗液环境下,考察了0～168 h内塑料仿真饰品中邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)和邻苯二甲酸二辛酯(DOP)3种增塑剂的迁移风险。结果表明微波萃取法的提取效率优于其余3种方法。所建立方法的定量限为5 mg/kg (邻苯二甲酸二异壬酯(DINP)、邻苯二甲酸二异癸酯(DIDP)为25 mg/kg),在0.1～50 mg/L(DINP、DIDP在0.5～250 mg/L)范围内,线性相关系数在0.99以上,在3个添加水平下的回收率在90.95%与98.67%之间。在模拟条件下,DEHP的迁移风险较高,浸泡72 h后约有0.75%溶出,而DBP和DOP的溶出风险较低。该法的灵敏度高、回收率高、选择性好,能满足实际工作的要求。     

液相色谱-串联质谱法测定饮料中邻苯二甲酸二(2-乙基)己酯和邻苯二甲酸二异壬酯

建立了饮料中邻苯二甲酸二(2-乙基)己酯(DEHP)和邻苯二甲酸二异壬酯(DINP)残留的液相色谱-串联质谱(LC-MS/MS)检测方法。2.0 g样品经8 mL甲醇振荡提取、定容、离心,取上清液过滤,采用LC-MS/MS电喷雾电离,多反应监测(MRM)模式对样品进行分析。DEHP在浓度范围为2～200μg/L,DINP在10～1000μg/L内线性良好,相关系数均大于0.998。实验表明:样品无明显的基质效应。样品中添加0.01～5 mg/kg的DEHP和DINP,其回收率为86.2%～111.6%;相对标准偏差(n=6)小于11%;DEHP检出限为0.008 mg/kg,定量限为0.01 mg/kg;DINP检出限为0.01 mg/kg,定量限为0.05 mg/kg。本方法提取效果好,具有良好的灵敏度、回收率和重复性,被成功用于实际饮料样品中DEHP和DINP的测定。     

Simultaneous determination of 17 phthalate esters in edible vegetable oils by GC‐MS with silica/PSA‐mixed solid‐phase extraction

A quantified method for the determination of 17 phthalate esters (PAEs) in edible vegetable oil by GC‐MS with the pretreatment of acetonitrile extraction and silica/N‐(n‐Propyl)ethylenediamine‐mixed SPE column was established. By the quantification of internal standard of D₄‐di(2‐ethylhexyl) phthalate, a good linearity range of related 17 PAEs was observed. The correlation coefficient was ranged at 0.994～1.000, and the standard lowest quantified level was 0.05～0.15 mg/L. The spiking recoveries of 17 PAEs were 78.3～108.9% with the relative standard deviations of 4.3～12.1% (n = 6). The method detection limits were 0.1～0.2 mg/kg. Meanwhile, PAEs were determined in 30 plastic buckets of edible vegetable oil from supermarkets in Hangzhou city of China. The survey of 30 oil samples showed di(2‐ethylhexyl) phthalate (DEHP) had the 100% (30/30) detection rate. The levels of diisobutyl phthalate with 86.7% (26:30), di‐n‐butyl phthalate (DBP) with 70% (21:30) and diethyl phthalate with 10% (3:30) were detected. It was worth note that DBP with 16.7% (5:30) samples and DEHP with 10% (3:30) samples were beyond the regular migrating limit, which indicated that more attention should be paid to the PAEs in oil with plastic package.     

基质固相分散-液相色谱-质谱法测定蔬菜中的邻苯二甲酸酯

采用基质固相分散-液相色谱-质谱法测定保护地蔬菜中邻苯二甲酸酯(PAEs)含量,并分析了蔬菜中PAEs污染状况,研究了水和洗涤液浸泡对蔬菜中PAEs的消除效果。蔬菜样品经弗罗里硅土和石墨化碳黑研磨均匀后,用乙酸乙酯淋洗净化,再用液相色谱/电喷雾质谱法测定。PAEs的添加回收率为82.7%~105.7%;RSD为1.7%~6.1%;检出限为邻苯二甲酸二甲酯(DMP):0.99ng;邻苯二甲酸二乙酯(DEP):0.75ng;邻苯二甲酸二丁酯(DBP):0.70ng;邻苯二甲酸二异辛酯(DEHP):1.9ng。本方法前处理简单,具有较高的准确度和灵敏度。黄瓜、番茄、西葫芦中4种PAEs总量分别为2.02、1.26、0.91mg/kg;洗涤实验结果表明,水和洗涤液浸泡可显著降低蔬菜中的PAEs含量。     

基于杯［6］芳烃萃取头的固相微萃取-气相色谱法测定啤酒中痕量的酞酸酯类化合物

选用自制杯［6］芳烃溶胶-凝胶固相微萃取(SPME)萃取头,建立了顶空SPME与气相色谱联用检测啤酒中8种酞酸酯(PAEs)的方法。采用L25(56)正交设计对萃取条件进行了优化,所得方法检出限为0.003～3.429 μg/L,相对标准偏差不超过13.5%,加标回收率为86.3%～109.3%。采用标准加入法对3种瓶装啤酒中PAEs进行了检测,结果表明邻苯二甲酸二(2-乙基己)酯(DEHP)是啤酒中最主要的酞酸酯类污染物,含量最高达5.24 μg/L。迁移试验表明,瓶装啤酒所用塑料垫圈中高含量的DEHP可能成为酒体中PAEs的一种来源,且延长贮存时间、提高贮存温度和振荡都能加快垫圈中DEHP的迁移。     

Quantitative determination of polycyclic aromatic hydrocarbons, polychlorinated biphenyls and organochlorine pesticides in sewage sludges using supercritical fluid extraction and mass spectrometric detection.

Supercritical CO2 extraction (SFE) proved to be a valuable, fast, quantitative and partly selective extraction technique for determining polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and chlorinated pesticides (OCPs) in sewage sludges of different catchment areas based on a comparison study with certified reference materials (CRMs) and on recovery data. Most PCB extracts could be measured directly after SFE whereas for PAHs a short clean-up improved the final separation by high-resolution capillary gas chromatography. Due to the amount of coextracted compounds and the low levels of OCPs, extracts obtained by SFE had to be submitted to a multistep clean-up for final measurement. Average concentrations of 6.9 mg/kg dry mass (dm) for the sum of the 16 Environmental Protection Agency PAHs, 0.1 mg/kg dm for the sum of the seven PCB congeners and 0.002-0.072 mg/kg dm for the OCPs were found in the sewage sludges. Compared to studies performed earlier in our laboratory PAHs are still present in similar concentrations whereas PCB levels have decreased significantly. OCPs could be detected in only low amounts. A correlation between sludge type and degree of contamination could only be found for PAHs.     

Development and validation of methods for the trace determination of phthalates in sludge and vegetables

A routine method which is simple, quick and precise has been set up and validated for phthalate analysis in environmental samples (tomato plants and sewage sludges). Six phthalates have been studied simultaneously: dimethylphthalate, diethylphthalate, di-n-butylphthalate, n-butylbenzylphthalate, di-2-ethyl-hexyl phthalate (DEHP) and di-n-octylphthalate. Optimization of sample, solvent extraction uses a Soxtec apparatus and extract purification with an a solid-phase extraction cartridge allows between 90 and 110% recovery of phthalates. Precise, sensitive and selective identification and quantifying of analytes is by GC-MS in the single ion monitoring mode. This protocol allows analytes with concentrations as low as 10 microg/kg dry matter (DM) to be determined from small (1-2 g DM) samples. This analytical method has been applied to the phthalate transfer study for agricultural recycling of sludges, where phthalate bioavailability has been studied in aquiculture using two types of experiments. Tomatoes have been grown in containers where the trace organics have been directly introduced as pure substances, and in a second experiment under the same growth conditions, sewage sludge has replaced the pure substances. Transfer of these trace organics has been followed into the various parts of the tomato plant and in general only the DEHP is worthy of note although its percentage transfer remains very low even in an experiment designed to maximize this.     

气相色谱-质谱法同时测定动物内脏中的14种酞酸酯类环境激素残留

开展了动物内脏中14种酞酸酯类（PAEs）环境激素残留的气相色谱-电子轰击离子源/质谱（GC-EI/MS）的分析方法研究。优化与选择了动物内脏样品的前处理条件,动物内脏样品经正己烷/二氯甲烷（1/1,v/v）混合提取剂超声提取、Florisil硅藻土固相萃取柱净化与乙酸乙酯/正己烷（2/3,v/v）混合洗脱剂洗脱和浓缩后,以邻苯二甲酸二苯基酯（DPhP）为内标物,采用GC-EI/MS的选择离子监测方式（SIM）进行定性和定量分析。当猪肝样品的加标浓度水平为100、200、400 μg/kg时,加标回收率为：60%~110%,相对标准偏差为：0.78%~10.3%;除邻苯二甲酸二（2-甲氧基乙基）酯（DMEP）与邻苯二甲酸二（2-乙氧基乙基）酯（DEEP）的检测限（MDL）分别为3.30与2.25 μg/kg外,其余的12种PAEs的MDL ≦ 1.74 μg/kg;线性范围为50 ~ 800 μg/kg,相关系数都大于0.9994。此分析方法成功地应用于6种动物内脏中14种痕量PAEs残留的分析。     

QuEChERS/高效液相色谱测定食品中17种邻苯二甲酸酯

建立了同时检测食品中17种邻苯二甲酸酯类化合物的QuEChERS/高效液相色谱分析方法.样品经乙腈提取,采用含50 mg PSA和150 mg MgSO4填料的净化管进行净化,分析液经C18柱分离,乙腈-水为流动相梯度洗脱,流速1.0 mL/min,紫外检测波长224 nm.在优化色谱条件下,DINP在0.5～10 m...     

Extraction and percolation of PAEs from chemical protective gloves

Phthalates (PAEs) have high solubility in polymers and are added as plasticisers to increase the flexibility and plasticity of polymeric materials. In this study, methanol, hexane, ethyl ether and acetone were used for the extraction of PAEs from chemical protective gloves at temperatures of 20–80 °C. DEHP (di-2-ethylhexyl phthalate) and DBP (di-n-butyl phthalate) were extracted from neoprene, nitrile and PVC glove samples using the above four solvents. The extraction level of DEHP from the glove samples was proportional to the Log K_ow values of the extraction solvents. This result implied that PAEs were more soluble in non-polar solvents and were likely to be extracted from the gloves. Increasing the extraction temperature resulted in a higher extraction of DBP and DEHP from the gloves. In the ASTM F739 permeation method, the aromatic solvents permeated through the glove samples and dissolved DEHP. If the permeant and DEHP had similar solubility parameters, DEHP was likely to be leached from the gloves. The modelling results indicated that the permeation behaviour of the organic solvent in the PVC glove was non-Fickian diffusion. It was speculated that the plasticiser increased the diffusion coefficients of the permeants in the PVC gloves. This study suggested that the potential dissolution and leaching of PAEs from chemical protective gloves should be a concern for workers who handle organic solvents.     

Evaluation of the Removal of Selected Phthalic Acid Esters (PAEs) in Municipal Wastewater Treatment Plants Supported by Constructed Wetlands

Phthalic acid esters (PAEs) have a negative impact on living organisms in the environment, therefore, are among the group of Endocrine Disrupting Compounds (ECDs). Unfortunately, conventional methods used in municipal wastewater treatment plants (MWWTPs) are not designed to eliminate PAEs. For this reason, the development of cheap and simple but very effective techniques for the removal of such residues from wastewater is crucial. The main aim of this study was the evaluation of the removal of six selected PAEs: diethyl phthalate (DEP), di-n-octyl phthalate (DOP), di-n-butyl phthalate (DBP), benzyl butyl phthalate (BBP), bis(2-ethylhexyl) phthalate (DEHP) and dimethyl phthalate (DMP), in real MWWTPs supported by constructed wetlands (MWWTP–CW system). For the first time, the possibility of using three new plants for this purpose, Cyperus papyrus (papyrus), Lysimachia nemorum (yellow pimpernel) and Euonymus europaeus (European spindle), has been presented. For determining the target PAEs in wastewater samples, a method of SPE (Solid-Phase Extraction)–GC–MS(SIM) was developed and validated, and for plant materials, a method of UAE (Ultrasound-Assisted Extraction)–SPE–GC–MS(SIM) was proposed. The obtained data showed that the application of the MWWTP–CW system allows a significant increase in the removal of DEP, DBP, BBP and DEHP from the wastewater stream. Euonymus europaeus was the most effective among the tested plant species for the uptake of analytes (8938 ng × g⁻¹ dry weight), thus, this plant was found to be optimal for supporting conventional MWWTPs.     

Multivariate optimization of a solid-phase microextraction method for the analysis of phthalate esters in environmental waters

A solid-phase microextraction method (SPME) coupled to gas chromatography-mass spectrometry (GC-MS) has been developed for the determination of the six phthalate esters included in the US Environmental Protection Agency (EPA) Priority Pollutants list in water samples. These compounds are dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), butylbenzyl phthalate (BBP), di-2-ethylhexyl phthalate (DEHP) and di-n-octyl phthalate (DOP). Detailed discussion of the different parameters, which could affect the extraction process, is presented. Main factors have been studied and optimized by means of a multifactor categorical design. Different commercial fibers, polydimethylsiloxane (PDMS), polydimethylsiloxane-divinylbenzene (PDMS-DVB), polyacrylate (PA), Carboxen-polydimethylsiloxane (CAR-PDMS) and Carbowax-divinylbenzene (CW-DVB), have been investigated, as well as the extraction mode, exposing the fiber directly into the sample (DSPME) or into the headspace over the sample (HS-SPME), and different extraction temperatures. The use of this experimental design allowed for the evaluation of interactions between factors. Extraction kinetics has also been studied. The optimized microextraction method showed linear response and good precision for all target analytes. Detection limits were estimated considering the contamination problems associated to phthalate analysis. They were in the low pg mL(-1), excluding DEHP (100 pg mL(-1)). The applicability of the developed SPME method was demonstrated for several real water samples including mineral, river, industrial port and sewage water samples. All the target analytes were found in real samples. Levels of DEP and DEHP were over 1 ng mL(-1) in some of the samples.     

固相萃取/高效液相色谱-串联质谱法测定罗非鱼中9种邻苯二甲酸酯

建立了罗非鱼中邻苯二甲酸二(2-甲氧基)乙酯(DMEP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸丁基苄基酯(BBP)、邻苯二甲酸二(2-丁氧基)乙酯(DBEP)、邻苯二甲酸二戊酯(DPP)、邻苯二甲酸二(4-甲基-2-戊基)酯(BMPP)、邻苯二甲酸二己酯(DHXP)、邻苯二甲酸二(2-乙基)己酯(DEHP)、邻苯二甲酸二正辛酯(DNOP)共9种邻苯二甲酸酯(PAEs)的高效液相色谱-串联质谱测定方法。样品经乙酸乙酯提取后,经LC-Si固相萃取柱净化,以甲醇和甲酸-乙酸铵缓冲溶液为流动相,梯度洗脱,采用HPLC-MS/MS电喷雾正离子(ESI+)电离,多反应监测(MRM)模式检测,基质匹配外标法定量。9种PAEs在1.0～200.0μg.L-1范围内均具有良好的线性关系,相关系数不低于0.991 8,平均加标回收率为75%～107%,批内、批间相对标准偏差分别在1.9%～11.8%和3.6%～13.1%之间。该方法具有简单、快速、灵敏度高和定性准确等优点,满足残留分析的要求。     

固相萃取-气相色谱法测定纺织品中的邻苯二甲酸酯类环境激素

采用索氏提取法以正己烷为提取溶剂提取纺织品中的邻苯二甲酸酯类物质(PAEs),以强阴离子交换固相萃取(SPE)小柱净化本底杂质并富集待测物,建立了纺织品中10余种PAEs环境激素的同时测定方法。采用的固相萃取条件为:5 mL正己烷活化、3 mL异辛烷淋洗、2 mL含15%乙酸乙酯的正己烷溶液洗脱。SPE能有效地对提取液进行富集浓缩,同时对纺织物提取液中的杂质净化效果突出。该方法准确可靠,重现性好,在5~100 mg/kg 添加水平,PAEs各化合物的回收率为86.3%~102.7%,相对标准偏差（RSD）一般小于5%。检测的10余种PAEs中邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丙酯(DPrP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二戊酯(DAP)、邻苯二甲酸丁基苄基酯(BBP)、邻苯二甲酸二环己酯(DCHP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)、邻苯二甲酸二正辛酯(DNOP)的方法检出限小于1mg/kg,邻苯二甲酸二异壬酯(DINP)与邻苯二甲酸二异癸酯(DIDP）的方法检出限分别为1.74 mg/kg和1.55 mg/kg。     

固相微萃取-气相色谱法测定白洋淀水样中的邻苯二甲酸酯类化合物

建立了固相微萃取(SPME)-气相色谱法(GC)分析环境水样中痕量邻苯二甲酸酯类化合物(PAEs)的方法。选用100 μm聚二甲基硅烷(PDMS)萃取纤维,在磁力搅拌条件下,对水样中的PAEs萃取富集60 min,然后直接注入GC进样口,在250 ℃温度下解吸4 min后进行分析测定,13种PAEs能得到充分提取和分离。方法的重现性(以相对标准偏差(RSD)计为0.2%～9.7%,检出限为0.02～0.83 μg/L。将本方法应用于白洋淀水样中PAEs的分析检测发现,样品中邻苯二甲酸二异丁酯(DIBP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)检出率相对较高。对水样进行两个浓度水平(2.5 μg/L和5.0 μg/L)的加标试验,加标回收率为75.3%～111.0%,RSD为2.1%～8.0%(n=3),能够满足环境水样中痕量PAEs的测定要求。     

Monitoring of di-(2-ethylhexyl)phthalate,nonylphenol, nonylphenol ethoxylates,and polychlorinated biphenyls in anaerobic and aerobic sewage sludge by gas chromatography–mass spectrometry

The occurrence of di-(2-ethyhexyl)phthalate (DEHP), nonylphenol and nonyphenol mono- and diethoxylates (NPEs) and seven polychlorinated biphenyl (PCB) congeners in different types of sludge samples is reported. The analysis of these compounds was carried out by sonication-assisted extraction and analytical determination by gas chromatography coupled with a mass spectrometry detector, following a previously described method. The applicability of the method was tested by monitoring the organic pollutants in primary, secondary, mixed, and digested-dehydrated sludge samples from two wastewater treatment plants (WWTPs) based on aerobic and on anaerobic biological stabilization. The occurrence of these compounds in sewage sludge and the influence of sludge stabilization process on the further farmland application of the sludge were evaluated. DEHP and NPEs were detected in all analysed sludge samples from both WWTPs at concentration levels in the range of 22.3–601?mg?kg^?1 and 136–2357?mg?kg^?1 dm (dry matter), respectively. PCBs were detected in all types of sludge analysed from the anaerobic WWTP but was not detected in any sludge sample from the aerobic WWTP. Concentration levels of the sum of the seven PCBs congeners were up to 1.5?mg?kg^?1 dm. The concentration of DEHP, sum of NPEs, and sum of the seven PCB congeners were higher than the limits fixed in the third draft of the future Sludge Directive for land application of sludge in the 67%, 100%, and 11% of samples from the anaerobic WWTP and in the 83%, 92%, and 0% of samples from the aerobic WWTP, respectively.     

Determination of phthalates in milk and milk products by liquid chromatography/tandem mass spectrometry

A liquid chromatographic/tandem mass spectrometric method using pneumatically assisted electrospray ionisation (LC/ESI-MS/MS) was developed for determination of dibutyl phthalate (DBP), benzyl butyl phthalate (BBP), di-2-ethylhexyl phthalate (DEHP), di-'isononyl' phthalate (DINP) and di-'isodecyl' phthalate (DIDP) in milk and milk products including infant formulas. The phthalates were extracted by a mixture of tert-butyl methyl ether and hexane from liquid samples. DBP, BBP and DEHP were removed from fats by liquid/liquid extraction into acetonitrile while DINP and DIDP were cleaned up on deactivated silica. The phthalates were detected in positive ion mode after separation on a reversed-phase C5 analytical column. Two transition products were monitored for each compound. The detection limits related to the transition products of lowest abundance were in the range 5-9 microg/kg.     

基质固相分散-气相色谱/质谱法测定蔬菜中的邻苯二甲酸酯

利用基质固相分散-气相色谱/质谱法测定了蔬菜中的邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、邻苯二甲酸丁基苄基酯和邻苯二甲酸二异辛酯。蔬菜样品经弗罗里硅土和石墨化炭黑研磨均匀后,用乙酸乙酯淋洗净化,结果表明:上述5种邻苯二甲酸酯在0.05~10.00 mg/L 范围内具有良好的线性,样品的添加回收率为76%~90%,相对标准偏差为2%~7%,5种邻苯二甲酸酯的检出限为0.01~0.024 mg/kg。该方法操作简便、经济,分析速度快,适用于大批量样品的分析。     

GC–MS法测定白酒中邻苯二甲酸二丁酯和邻苯二甲酸二(2-乙基)己酯

采用正己烷提取白酒中的邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二(2-乙基)己酯(DEHP),建立了气相色谱–质谱法测定白酒中DBP,DEHP残留量的检测方法。对氮吹、水浴、盐析和直接提取4种方法的提取效率进行考察,选择氮吹法处理样品。在0.20~20 mg/L范围内DBP,DEHP的质量浓度分别与色谱峰面积呈良好的线性关系,线性相关系数分别为0.999 3,0.999 8。方法的定量限(S/N=10)为0.04 mg/kg,加标回收率在82.0%~92.5%之间,测定结果的相对标准偏差为1.91%~4.83%(n=6)。该方法适合白酒中DBP,DEHP残留量的日常检测。     

毛细管气相色谱法测定化妆品中的酞酸酯

建立了用毛细管气相色谱配氢火焰离子化检测器测定化妆品中6种酞酸酯(邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸丁基苄基酯(BBP)、邻苯二甲酸二(2-乙基己)酯(DEHP)和邻苯二甲酸二正辛酯(DOP))的方法。样品用甲醇超声提取,经高速冷冻离心,清液经干燥脱水过0.5 μm滤膜过滤,直接注入气相色谱仪进行分析。然后,经过气相色谱-电子电离-质谱检测分析,确证气相色谱-氢火焰检测的阳性检出结果。用保留时间定性,外标法定量。6种酞酸酯的回收率为82.90%～